Method of producing low-glare coatings



Nov. 1, 1949.

F. H. NICOLL I'AL METHOD OF PRODUCING LOW-QLARE COATINGS Filed Aug. 18, 1944 2.8 2.9 '/m e5 x 103 Fem] E c@ Patented Nov. i, i949 aan METHOD OF PRODUCING LOW-GLARE y COATINGS Frederick H. Nicoll and Ferd E. Williams, Princeton, N. J., assignors to Radio Corporation of America, a corporation of Delaware Application August 18, 1944, Serial No. 550,080

7 Claims.

Serial N0. 461,958, led October 14, 1942, now

Patent No. 2,461,840, dated February 15, 1949, the low reflective film preferably should have a thickness of the order of an odd number of quarter wavelengths of light of a selected wavelength.

Skeletonized silica lms on glass have been produced heretofore by the use of hydrouoric acid vapor and by the Vapor of hydrouosilicic acid. In this way, a large variety of glasses have been treated so as to reduce or eliminate reilection from the treated surface. It has been recognized for some time, however,

that a solution method of treatment would have certain adv vantages not inherent in the acid vapor method of treatment. For example, the vapor method of coating usually produces a coating on only one surface while a solution method is readily utilized to coat all surfaces of the object. The solution method also involves no temperature differential between the solution and the object treated and is otherwise more readily practiced than some of the vapor processes heretofore used.

The invention will be better understood from the following description considered in connection with the accompanying drawings and its scope is indicated by the appended claims.

Referring to the drawings:

Figure 1 is a curve showing the variation in the amount of glass dissolved with the time that the glass is maintained in a 16% fluosilicic acid solution at 45 C.,

Figure 2 illustrates the effect of acid concentration on the time required to form a non-reflective coating of predetermined thickness, and

Figure 3 is a pair of curves showing certain relations between temperature and the time required to produce a non-reflective coating.

The solution method of the present invention involves in general, a treating solution made by digesting or dissolving glass of the type to be treatedin fluosilicic acid or the equivalent until the solution reaches a point such that it selectively removes the non-film forming constituents of the treated glass surface and produces a skeletonized film or coating of the remaining constituents of the glass surface.

As applied to silica glasses, this means that silica glass, or its equivalent, is dissolved in fluosilicic acid (HzSiFs), that the non-siliceous constituents are differentially leached out or dissolved from the treated surface and that the resulting coating is skeletonized and altogether or largely constituted of silica.

Thus it is found, for example, that a solution suitable for producing a low index lm on window glass and the like is made from 600 c.c. of 16% uosilicic acid (HzSiFs) in which is maintained a temperature of 45 C. a piece of window glass having a total surface area of about three square feet.

The pieces of glass in the solution of fluosilicic acid plus glass are periodically examined and their characteristic appearance indicates the progress of formation of the iinal treating solution. These steps are as follows: Soon after placing the glass in solution the pieces are observed to have been strongly eaten away by the acid, but lunlike the ordinary etching of glassv with hydroiiuoric acid, the surface still has a polished appearance. At this point, any glass .protruding into the vapor arising from the solution will have a low reflection lm on it.` As the digestion of the glass continues the attack on the glass in solution becomes less and less film is formed in the vapor arising from the solution. As this condition is reached (after several hours), it is observed that a low reflection film is formed on the glass at the meniscus and in any trapped volumes (regions where two pieces of glass almost touch thus including a small volume of acid in contact with a large area of glass). These trapped volumes are the first regions to reach the correct conditions for producing low reflection films. When the time of digestion is further continued, the exposed surfaces ofthe glass begin to show interference colors but the reflection is still not low since the non-siliceous material is not yet completely removed and the lm has an index of refraction probably around 1.4.

After a further period of digestion, the glass surface becomes more highly colored with corresponding indications of low refractive index in the surface film.

At this point, the undissolved glass is removed and the solution is ready for producing a lowreflecting lm on a new piece of glass which is immersed in the solution at this point. Such a solution produces a. film of low reflection to green light in about one-half hour. This iilm is on both surface goes through the various sides of the glass and is satisfactory with respect to hardness and other mechanical properties.

The preparation of a treating solution as described is typical of the method in which glass is digested in an acid in order to bring about changes in the solution which will eventually produce a solution capable of selectively removing the non-siliceous parts of the glass. In general, tests performed on the glass at various times after mixing will give the results described above.

The method of preparing a treating solution may also consist of digesting glass in a mineral acid to which has been added a small quantity of hydrouoric acid. The digestion of the glass stages described above until satisfactory low index lms are obtained. Low reflection films have been obtained using acids such as H2SO4, HC1, HNOs, H3PO4, and also with salts of these acids. In each case it is essential thatsome HF be added. These acids even when hot will not produce low index films of low reflection on crown or lime glasses.

The mechanism of formation of the low index skeletonized film seems to depend on some action by the HF. This acid seems to remove enough silica so that the other mineral acid present is able to remove the non-siliceous component which, without the presence of HF, it would not be able to do to any great extent.

Still another method of preparing a treating solution is to mix a mineral acid with fluosilicic acid. As in the previously described cases, there is added to this mixture either dissolved glass of the nature desired to be given low reiiection properties, or, stated in different terminology, the ingredients which it is desired to retain on the low-reiiective glass surface. As in the previous cases mentioned, this would involve for silica glass, the addition of silica, and sodium and calcium ions.

The digestion of the glass appears to be merely a and fluoride ion concentration and in addition the amount of salts in solution. These two quantities will not be the same for treating different glasses but a solution being prepared by glass digestion will, after a certain length of time treat one type of glass whereas further digestion may be necessary to reach the point at which another type of glass can be treated. Thus, for example, a solution of lead glass digested in iiuosilicio acid reaches at some later time a condition in which it will satisfactorily treat lime glass.

The necessity for dissolving in the solution glass of the type which is to be coated may be avoided if the solution is made to have the desired constituents by dissolving the required ingredients in it. Thus, a solution suitable for in the acid solutions treating silica glass is made by dissolving in fluosilicic acid, silica and sodium and calcium fluosilicates.

Fig. 1 shows the variation in the amount of glass dissolved with the time that the glass is in a 16% fiuosilicic acid solution at 45 C. The velocity of a liquid-solid interface reaction can be expressed in the following form.

where =the solubility of the solid in the liquid c=the concentration of the solute in the solution -at time, t =the order of the reaction By graphical differentiation of the curve of concentration of dissolved glass versus time of immersion and plotting log EL) dt against log (zr-c), the process of solution has been found to be best described as a second order reaction, particularly if the solubility of the glass in the acid is taken as 24 mg./ml. Actually, the order of the reaction appears to be changing with time, especially when the solution approaches saturation. This indicates that the actual mechanism of solution is changing with the amount of dissolved glass. After 15 hours the mechanism has sufficiently changed so that silica is no longer being dissolved as rapidly as the metal oxides. and a silica film results. At-this stage, the 16% uosilicic acid solution contains approximately 20 mg. of glass per ml. of solution. From chemical analysis of the actual glass dissolved about 63% (12.5 mg.) is silica and about 37% (7.5 mg.) are metal oxides.

The time required to form a quarter wave film was determined as a function ofacid concentration. From the results shown in Fig. 2, it is apparent that the process of film formation is a. second 'order reaction. This confirms the less direct measurements made on the iluosilicic acid vapor process. As also shown in this figure, the time required to form a The iiuosilicic acid vapor process is not suitable for use at other than room temperature. This is method of altering pH l by making a film within an hour after the not the case for a solution process. Most of the work on the fluosilicic acid solution method has been done at 45 C. as a matter of convenience of experiment and because of the relatively short time required to make a quarter-wave lm. For example, above 50 C. ceresin wax containers melt and above 55 C. the Harvel insulating varnish used shows evidence of attack in the vapor proc-y ess by 16% iluosilicic acid. Therefore, in investigating the process as a function of temperature,

a platinum distillation flask of ml. capacity was used. A 16% solution prepared at 45 C. was found to produce low-index lms between 35 C. and 55 C. Below 35 C. thesolution failed to attack the glass at all, whereas above 55 C. the solution removed glass uniformly and produced only a narrow film at the meniscus.

The temperature dependence of the time required to make a quarter-wave film is shown by curve l in Figure 3. The heat of activation of the process of film formation can be calculated from this curve and is found to be the same as the heat of activation for lm formation by the vapor process.

ms@ =15.1 K en.

One way of preparing a solution to treat glass above 55 C. is to add alkali solution to the 16 percent fluosilicic acid working solution prepared at 45 C. The following table gives the volume of 10 NNaOH required to make 100 ml. of the 45 C. solution workat the specified temperature. The time to produce a quarter-wave lm is also included. In most cases the solution was tested alkali addition, and the resulting lms were not always completely uniform.

Temper- Vol.

ature NNaoH Tme C. MI. Mn 60 2 13 65 4 10. 5 70 .8 8. 5 75 1. 2 6. 5 80 1. 6 5 85 2. 6 4 90 5. 2 3 95 7. 0 2. 5 100 8. 5 2

been added at each experimental point. It is interesting to note that if curve I is continued to 100 C. the time of treatment would be one minute. At 100 C. curve 2 indicates two minutes and it can be calculated from the amount of alkali added that about half the fluosilicic acid has been changed to uosilicate at this temperature. This agrees with the previous results shown in Figure 2 that the time of treatment varies inversely with acid concentration. Also, it can be concluded that the heat of activation and therefore the .mechanism are independent of temperature.

During the treatment, the glass is supported at any convenient point in the liquid but not touching the bottom of the container or the surface of the liquid. A satisfactory means of support is a cradle or framework touching only the edges of the treated glass. t

The temperature of the solution during treatment of the glass is not critical. Good non-reflective films have been made at 100 C.vin one or two minutes. Evaporation of the solution at this temperature and the difficulty of nding suffciently rugged containers, however, make it desirable to operate at a lower temperature of the order of 65 C., for example.

We claim as our invention: l

1. The method of forming on the surface of a silica glass object a low-reiiectance skeletal film consisting essentially of silica and having a thickness of the order of an odd number of quarter wave lengths of light, said method comprising dissolving in a solution includinguosllicic acid about 20 mg. per ml. of a soda-lime-silica glass, said dissolved glass comprising about 63 per cent silica and about 37 per cent metallic oxides and immersing said object in said solution until said loW-reiiectance film is formed.

2. The method of claim 1 in which there is also present in said solution a mineral acid.

3. The method of forming on the surface of a silica glass object a low-reectance skeletal film consisting essentially of silica and having a thickness of the order of an odd number of quarter wave lengths of light, said method comprising dissolving in a solution including a mineral acid and a minor amount of hydrouoric acid about 20 mg. per m1. or a soda-lime-silica glass. said dissolved glass comprising about 63 per cent silica and about 37 per cent metallic oxides and immersing said object in said solution until said low-reflectance iilm is formed.

4. The method of forming on the surface of a silica glass object a low-reflectance skeletal film consisting essentially of silica and having a desired thickness of the order of an odd number of quarter wave lengths of light, said method comprising immersing partially in a solution including uosilicic acid a piece of a silica-containing glass, continuing said immersion until there is formed on a surface of said glass protruding above said solution a film having said desired thickness, removing the glass thus treated, immersing in said solution a fresh piece of a silicaglass, and continuing said last immersion until said fresh piece of glass has acquired a low reiiectance surface iilm having said desired thickness. v

5. A method' according to claim 4 in which said last mentioned glass is a soda, lime glass.

6. A method according to claim v4 in which said solution also contains a mineral acid,

7. In the production of a low-reflectance skeletal lm consisting essentially of silica and having a desired thickness of the order of an odd number of quarter wave lengths of light, said method comprising immersing partially in a solution comprising a mineral acid and a minor proportion of hydrouoric acid a piece of a silica-containing glass, continuing said immersion until there is formed on a surface of said glass protruding above said solution a film having said desired thickness, removing the glass thus treated, immersing in said solution a fresh piece of a silica-containing glass and continuing said immersion until said fresh piece of glass has acquired a low reflectance film having said desired thickness.

FERD E. s. REFERENCES CITED FREDERICK H. NICOLL.

WILLIAM The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Watts: Dictionary of Chemistry, vol. 2, 1889, pub. Longmans, Green & Co., N. Y. C., page 559.

Mellor: Treatise on Inorganic Chemistry, volume VI, page 942, pub. Longmans, Green and Co., 1925. 

